WO2008044329A1 - Spectrophotometer - Google Patents

Spectrophotometer Download PDF

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Publication number
WO2008044329A1
WO2008044329A1 PCT/JP2007/001048 JP2007001048W WO2008044329A1 WO 2008044329 A1 WO2008044329 A1 WO 2008044329A1 JP 2007001048 W JP2007001048 W JP 2007001048W WO 2008044329 A1 WO2008044329 A1 WO 2008044329A1
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WO
WIPO (PCT)
Prior art keywords
sample
liquid sample
light
window plate
spectrophotometer
Prior art date
Application number
PCT/JP2007/001048
Other languages
French (fr)
Japanese (ja)
Inventor
Yasuo Tsukuda
Original Assignee
Shimadzu Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by Shimadzu Corporation filed Critical Shimadzu Corporation
Priority to CN2007800369067A priority Critical patent/CN101523191B/en
Priority to JP2008538562A priority patent/JP4853518B2/en
Priority to US12/444,308 priority patent/US8049884B2/en
Priority to EP07827827.2A priority patent/EP2071317B1/en
Publication of WO2008044329A1 publication Critical patent/WO2008044329A1/en

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/251—Colorimeters; Construction thereof
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/01—Arrangements or apparatus for facilitating the optical investigation
    • G01N21/03—Cuvette constructions
    • G01N21/0303—Optical path conditioning in cuvettes, e.g. windows; adapted optical elements or systems; path modifying or adjustment
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/01—Arrangements or apparatus for facilitating the optical investigation
    • G01N21/03—Cuvette constructions
    • G01N2021/0346—Capillary cells; Microcells
    • G01N2021/035—Supports for sample drops
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2201/00—Features of devices classified in G01N21/00
    • G01N2201/06—Illumination; Optics
    • G01N2201/066—Modifiable path; multiple paths in one sample
    • G01N2201/0668—Multiple paths; optimisable path length

Definitions

  • the present invention relates to a spectrophotometer that irradiates a liquid sample with light and measures the transmitted light, and more particularly, a spectrophotometer suitable for measuring the transmission characteristics of a liquid sample that is a trace amount. About.
  • a spectrophotometer such as a general-purpose ultraviolet-visible spectrophotometer that has been widely used in the past, for example, light emitted from a light source is wavelength-dispersed by a spectroscope to extract measurement light having a specific wavelength.
  • An optical system is used that irradiates the measurement light to a sample installed in the sample chamber and detects the light that has passed through the sample.
  • sample cells, sample exchange mechanisms, and the like are installed in the sample chamber according to the purpose of analysis and the type of sample (see, for example, Patent Document 1).
  • transmission characteristics such as transmittance and absorbance of a liquid sample
  • a typical cuvette cell has an internal volume of several milliliters or more, and it is necessary to prepare a sufficient amount of liquid sample to satisfy this.
  • the sample cell for measuring a trace liquid sample described in Patent Document 2 is a capillary cell that sucks and holds a liquid sample by using a capillary phenomenon, but even in the case of such a capillary cell, there are generally several UL The amount of liquid above is necessary, It cannot cope with the analysis of a liquid sample having a smaller liquid volume. In addition, there are problems with the liquid cell such that the injection of the liquid sample into the cell is troublesome and the cleaning after the measurement takes time.
  • the upper side base portion 40 When the liquid sample is set, the upper side base portion 40 is retracted upward, for example, and the liquid sample is dropped on the upper end surface of the light receiving side optical fiber 43. Thereafter, the upper base 40 is once lowered to a height at which the lower end surface of the light emitting side optical fiber 41 almost comes into contact with the upper end surface of the light receiving side optical fiber 43 (see Fig. 9 (a)), and then the upper side. The base 40 is raised to a predetermined height. As a result, the liquid sample S between the lower end surface of the light emitting side optical fiber 4 1 and the upper end surface of the light receiving side optical fiber 43 has a drum shape whose center is constricted by the surface tension as shown in Fig. 9 (b). It will be bridged up and down.
  • the liquid sample S is connected between the light projecting side optical fiber 4 1 and the light receiving side optical fiber 4 3, and the measurement light transmitted through the light projecting side optical fiber 41 is It passes through the liquid sample S and is sent into the light receiving side optical fiber 43.
  • the optical path length in a liquid sample is set to about 1 mm, and it is said that analysis of a very small amount of liquid sample of about 1 to 21_ is possible.
  • Patent Document 1 Japanese Patent Laid-Open No. 5-3 1 5324
  • Non-Patent Document 1 “NanoDrop ND-1000 Overview”, [online], US Nanodrop Technologies, [September 1996 25] Day search], Internet URL: http: / / www. Nanodrop. Com / nd-1000-overvi ew. Html>
  • the present invention has been made in view of the above problems, and the object of the present invention is to provide a simple and inexpensive configuration and easy measurement of transmission of a very small amount of liquid sample of about 1 to 2 L or less. It is to provide a spectrophotometer for measuring a small amount of liquid sample that can be carried out by simple operation.
  • the present invention made to solve the above-described problems includes an optical system that forms a measurement light passage in the vertical direction in a space, and a liquid sample that is inserted into the measurement light passage by the optical system.
  • a spectrophotometer for measuring the transmission characteristics of the liquid sample wherein the sample holding unit comprises:
  • a sample stage made of a material that can transmit light, and whose upper and lower surfaces are both horizontal;
  • a window made of a material capable of transmitting light and held on the sample stage so as to form an interface parallel to the upper surface with a predetermined distance on the liquid sample dropped on the upper surface of the sample stage.
  • the lower surface of the window plate is brought close to a position at a predetermined distance from the upper surface of the sample table.
  • the measurement light is irradiated from above or below to measure the light transmitted downward or upward.
  • the material constituting the sample stage and the window plate be as highly translucent as possible.
  • the liquid sample liquid It must be hard enough not to be deformed by the weight of the drop.
  • quartz glass may be used as the material.
  • a glass or plastic optical fiber can be cut into an appropriate length and used as a sample stage.
  • the window plate that sandwiches the liquid sample from above and below and the sample stage are placed in the passage of measurement light in the space, so that the measurement light moves the sample up and down (from top to bottom or vice versa).
  • the above predetermined distance becomes the optical path length of the measurement.
  • the liquid sample held in the sample holder is 1 to
  • a trace amount of about 2 UL or less is sufficient, it is suitable for analyzing a trace amount liquid sample such as a biological sample.
  • the liquid sample only needs to be dropped on the upper surface of the sample stage as a sample preparation, so the work involved in the analysis is very simple and labor-saving.
  • the parts that come into contact with the liquid sample such as the upper surface of the sample stage and the lower surface of the window plate, are flat, so that wiping and cleaning with a cleaning solution can be performed easily and are easy to dry.
  • the configuration for holding the liquid sample between the end faces of the optical fiber as described above.
  • the liquid sample does not come into contact with the main body of the measurement optical system or the like, it is difficult to damage or contaminate the expensive main body of the apparatus, and the burden of maintenance and inspection does not increase.
  • it is not necessary to move the optical system that forms the measurement light path in order to set the sample or replace the sample so the measurement optical system can be fixed and simple in structure and can be inexpensive.
  • sample replacement is easy either manually or automatically, and analysis throughput can be improved.
  • the distance between the window plate and the sample table is gradually narrowed, and the sample table and the window plate itself or those are used as the regulating member.
  • the distance can be set with high accuracy by stopping the narrowing of the distance when the member holding the contact is made.
  • the measurement optical path length is determined with high accuracy and the measurement accuracy can be improved, and the cost is reduced because the structure is simple and high positioning accuracy is not required for stopping operation of, for example, the window plate moving mechanism. It is also effective.
  • the measurement optical path length is shortened, and when the sample concentration is low and the absorbance per unit length is small, the measurement optical path length is short. Measuring accuracy can be improved by ensuring a long period of time. Therefore, in the configuration of the above aspect, if the height of the regulating member can be changed to change the predetermined distance, the measurement optical path length can be easily changed. With these changes, the measurement optical system may be exactly the same, and it is necessary to prepare multiple sample cells with different optical path lengths, such as cuvette cells. Therefore, the change in the measurement optical path length can be realized with a small increase in cost.
  • FIG. 1 is a top plan view (a) of a pedestal portion of a sample holder used in a spectrophotometer according to an embodiment of the present invention, and (b) an end view taken along line ⁇ _ ⁇ ′.
  • FIG. 2 is a schematic side view for explaining a procedure for setting a liquid sample in the sample holder shown in FIG.
  • FIG. 4 is an overall configuration diagram of the optical system of the spectrophotometer of the present embodiment.
  • FIG. 5 is a plan view of the rotating plate for changing the measurement optical path length as viewed from above.
  • FIG. 6 Top view (a) and front view (b) of another configuration for changing the measurement optical path length.
  • FIG. 7 is a control block diagram of a spectrophotometer based on the optical system shown in FIG.
  • FIG. 8 is a top plan view of the pedestal of the sample holder in the spectrophotometer of another embodiment (a
  • FIG. 9 is an explanatory diagram of a conventional method for holding a trace liquid sample.
  • FIG. 1 is a top plan view (a) of the pedestal 20 of the sample holder and an end view (b) along the line A_A ′.
  • FIG. 2 is a schematic side view for explaining the procedure for setting the liquid sample in the sample holder.
  • the thickness d 3 of the substrate 21 is 2 mm
  • the diameter d 1 of the light guide 22 is 0.8 to 1. O mm. This diameter d 1 is taken into account so that the liquid sample can maintain a granular state on its surface.
  • the measurement optical path length depends on the height d 4 of the spacer 23, as described above, for example, as shown in Fig. 3 (c), the spacer 2 3 'has a different height.
  • the measurement optical path length can be easily changed.
  • the optical path length is extended to L2.
  • the entire height can be increased by inserting another auxiliary spacer 24 on the spacer 23 as shown in Fig. 3 (b). You may make it change the length.
  • the optical path length is suitably in the range of about 0.2 to 0.7 mm.
  • the liquid sample S thus prepared is irradiated with measurement light from directly above through the translucent cover plate 25.
  • the wavelength component corresponding to the sample component in the sample S is absorbed, and the transmitted light is guided to the light guide 2 It goes out downward through 2.
  • most of the unnecessary light such as scattered light is blocked by the light-blocking substrate 21 and therefore does not exit downward.
  • the transmitted light is collected by the lens 1 2 at the detector 1 1, and after the light region is limited by the slit 1 3, the diffraction grating
  • the transmitted light is wavelength-dispersed by the diffraction grating 14, and the wavelength-dispersed light is detected almost simultaneously by a multi-channel detector 15 such as a C CD linear sensor.
  • a multi-channel detector 15 such as a C CD linear sensor.
  • the configuration of the optical system can be changed as appropriate, such as turning the diffraction grating 14 to an optical system that scans the wavelength of light incident on the detector 15.
  • a double beam configuration is also possible.
  • the detector 15 can obtain a detection signal reflecting the transmission characteristics of the liquid sample S as described above, an absorption spectrum having a predetermined wavelength range, for example, can be obtained in a signal processing unit described later. Can be created.
  • a skirt portion 27 having a conical peripheral surface is provided around a cylindrical light guide 22 protruding upward from the substrate 21.
  • the light guide 2 2 and the skirt 2 7 may be integrated or separated. This configuration makes it difficult for the waste to get caught in the corner on the upper surface of the light guide 22, ensuring smooth movement of the wiping head and attaching the waste fibers to the light guide 22. Can also be prevented.
  • the dropping of the liquid sample is performed by the operator, and is not automated. This is because collecting and dropping a very small amount of a liquid sample of about 1 L or less using a micropipette is generally difficult with an inexpensive apparatus, but of course, this may be automated.

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  • Physics & Mathematics (AREA)
  • Biochemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Investigating Or Analysing Materials By Optical Means (AREA)
  • Optical Measuring Cells (AREA)

Abstract

When a liquid sample is dropped onto the upper surface of a transparent columnar photoconductor (22), the liquid sample is held in a granular state by surface tension. When a translucent cover plate (25) is lowered down to a position where the lower surface abuts against a spacer (23), the liquid sample is held in a narrow gap formed between the upper surface of the photoconductor (22) and the lower surface of the translucent cover plate (25). The liquid sample thus held is irradiated with measurement light from right above and the transmitted light passed through the liquid sample and exited downward through the photoconductor (22) is introduced to a spectral detecting section and subjected to spectrometry. The measurement optical path length can be adjusted by the height of the spacer (23). Consequently, transmission spectrometry of a trace of liquid sample can be performed conveniently.

Description

明 細 書  Specification
分光光度計  Spectrophotometer
技術分野  Technical field
[0001 ] 本発明は、 液体試料に光を照射してその透過光を測定する分光光度計に関 し、 さらに詳しくは、 微量である液体試料の透過特性を測定するのに好適な 分光光度計に関する。  TECHNICAL FIELD [0001] The present invention relates to a spectrophotometer that irradiates a liquid sample with light and measures the transmitted light, and more particularly, a spectrophotometer suitable for measuring the transmission characteristics of a liquid sample that is a trace amount. About.
背景技術  Background art
[0002] 従来から広く利用されている汎用的な紫外可視分光光度計等の分光光度計 では、 例えば、 光源から出射した光を分光器により波長分散させて特定の波 長を有する測定光を取り出し、 その測定光を試料室内に設置された試料に照 射して該試料を通過した光を検出する、 という光学系が利用される。 そして 、 分析目的や試料の種類などに応じて試料室内には様々な形態の試料セルや 試料交換機構などが設置されるようになっている （例えば特許文献 1など参 照） 。 例えば液体試料の透過率や吸光度などの透過特性を測定する際には、 液体試料を収容する角形状或いは円筒形状のキュベットセルを用いるのが一 般的である。 一般的なキュベットセルの内容積は数 m L以上であり、 これを 満たすために十分な量の液体試料を用意する必要がある。  In a spectrophotometer such as a general-purpose ultraviolet-visible spectrophotometer that has been widely used in the past, for example, light emitted from a light source is wavelength-dispersed by a spectroscope to extract measurement light having a specific wavelength. An optical system is used that irradiates the measurement light to a sample installed in the sample chamber and detects the light that has passed through the sample. Various types of sample cells, sample exchange mechanisms, and the like are installed in the sample chamber according to the purpose of analysis and the type of sample (see, for example, Patent Document 1). For example, when measuring transmission characteristics such as transmittance and absorbance of a liquid sample, it is common to use a square or cylindrical cuvette cell that accommodates the liquid sample. A typical cuvette cell has an internal volume of several milliliters or more, and it is necessary to prepare a sufficient amount of liquid sample to satisfy this.
[0003] 近年、 蛋白質や D N Aの定量などの生化学分野で上記のような紫外可視分 光光度計が利用されることが多くなつているが、 こうした際に分析対象とさ れる液体試料はその量が極めて少ないことが多い。 特に D N A関連の分析に おいては、 試料が貴重で且つ高価であるため、 数； U L以下の液体試料で分析 を行う必要がある場合もある。 こうした微量の液体試料を分析する目的では 上記のようなキュベットセルは使用できない。 そこで、 こうした微量な液体 試料を分光測定するために適した容器が従来より知られている。  [0003] In recent years, the UV-visible spectrophotometer as described above is often used in the field of biochemistry such as protein and DNA quantification. The amount is often very small. Especially for DNA-related analysis, the sample is valuable and expensive, so it may be necessary to perform analysis on a liquid sample of a few; UL. The cuvette cell as described above cannot be used for the purpose of analyzing such a small amount of liquid sample. Therefore, a container suitable for spectroscopic measurement of such a small amount of liquid sample has been conventionally known.
[0004] 例えば特許文献 2などに記載の微量液体試料測定用試料セルは、 毛細管現 象を利用して液体試料を吸い上げて保持するキヤビラリセルであるが、 こう したキヤビラリセルの場合でも、 一般に数； U L以上の液量が必要であって、 これよりも少ない液量の液体試料の分析には対応できない。 また、 キヤビラ リセルではセル内への液体試料の注入が面倒であったり、 測定後の洗浄に手 間が掛かったりするという問題もある。 [0004] For example, the sample cell for measuring a trace liquid sample described in Patent Document 2 is a capillary cell that sucks and holds a liquid sample by using a capillary phenomenon, but even in the case of such a capillary cell, there are generally several UL The amount of liquid above is necessary, It cannot cope with the analysis of a liquid sample having a smaller liquid volume. In addition, there are problems with the liquid cell such that the injection of the liquid sample into the cell is troublesome and the cleaning after the measurement takes time.
[0005] 一方、 1 L程度のごく微量な液体試料の分光測定を可能とした装置とし て、 米国ナノ ドロップテクノロジーズ社が販売している分光光度計 N D _ 1 0 0 0が知られている （非特許文献 1参照） 。 この分光光度計における試料 保持部の概略構成を図 9に示す。 この試料保持部では、 上部側基部 4 0によ り保持された投光側光ファイバ 4 1の下向きの端面と下部側基部 4 2により 保持された受光側光ファイバ 4 3の上向きの端面とが上下方向に対向するよ うに配置されている。 下部側基部 4 2は位置が固定であるのに対し、 上部側 基部 4 0は上下方向に移動可能である。  [0005] On the other hand, a spectrophotometer ND _ 1 100 0 sold by Nanodrop Technologies in the United States is known as a device that enables spectroscopic measurement of a very small amount of liquid sample of about 1 L ( Non-patent document 1). Figure 9 shows the schematic configuration of the sample holder in this spectrophotometer. In this sample holder, the downward end surface of the light projecting side optical fiber 41 held by the upper side base portion 40 and the upward end surface of the light receiving side optical fiber 43 held by the lower side base portion 42 are formed. They are arranged so as to face each other in the vertical direction. The lower base portion 42 is fixed in position, whereas the upper base portion 40 is movable in the vertical direction.
[0006] 液体試料をセッ卜する際には上部側基部 4 0は例えば上方に退避され、 受 光側光ファイバ 4 3の上端面上に液体試料が滴下される。 その後、 投光側光 ファイバ 4 1の下端面が受光側光ファイバ 4 3の上端面に殆ど接触する高さ まで上部側基部 4 0は一旦降下され （図 9 ( a ) 参照） 、 それから上部側基 部 4 0は所定高さまで引き上げられる。 これにより投光側光ファイバ 4 1の 下端面と受光側光ファイバ 4 3の上端面との間で液体試料 Sは、 図 9 ( b ) に示すように、 表面張力によって中央がくびれた鼓形状で上下方向に橋架さ れる。  When the liquid sample is set, the upper side base portion 40 is retracted upward, for example, and the liquid sample is dropped on the upper end surface of the light receiving side optical fiber 43. Thereafter, the upper base 40 is once lowered to a height at which the lower end surface of the light emitting side optical fiber 41 almost comes into contact with the upper end surface of the light receiving side optical fiber 43 (see Fig. 9 (a)), and then the upper side. The base 40 is raised to a predetermined height. As a result, the liquid sample S between the lower end surface of the light emitting side optical fiber 4 1 and the upper end surface of the light receiving side optical fiber 43 has a drum shape whose center is constricted by the surface tension as shown in Fig. 9 (b). It will be bridged up and down.
[0007] したがって、 投光側光ファイバ 4 1 と受光側光ファイバ 4 3との間を液体 試料 Sで連結したような状態となり、 投光側光ファイバ 4 1中を送られてき た測定光は液体試料 Sを通過して受光側光ファイバ 4 3中に送り込まれる。 通常、 液体試料中の光路長は 1 m m程度に設定されており、 1〜2 1_程度 のごく微量の液体試料の分析が可能であるとされている。  [0007] Therefore, the liquid sample S is connected between the light projecting side optical fiber 4 1 and the light receiving side optical fiber 4 3, and the measurement light transmitted through the light projecting side optical fiber 41 is It passes through the liquid sample S and is sent into the light receiving side optical fiber 43. Normally, the optical path length in a liquid sample is set to about 1 mm, and it is said that analysis of a very small amount of liquid sample of about 1 to 21_ is possible.
[0008] しかしながら、 この分光光度計では、 投光側光ファイバ 4 1の光軸と受光 側光ファイバ 4 3の光軸とがー致しないと光量の損失が発生するため、 上部 側基部 4 0を上下動させる機構の精度ゃ両基部 4 0、 4 2の位置精度を十分 に高くする必要があり、 その分コストが高いものとなる。 また、 測光光学系 を構成する光ファイバ 4 1、 43と液体試料 Sとが直接接触するため、 前述 の如く例えば試料室内空間などの測定光経路中に試料セルを挿入するような 場合に比べて、 試料の交換が遙かに面倒で手間が掛かり、 自動的に試料を交 換しながら多数の試料の測定を行うような場合に時間が掛かる。 [0008] However, in this spectrophotometer, if the optical axis of the light projecting side optical fiber 41 and the optical axis of the light receiving side optical fiber 43 do not match, a loss of light amount occurs. The precision of the mechanism that moves the base up and down requires that the positional precision of both bases 40 and 42 be sufficiently high, which increases the cost. Photometric optics Since the optical fibers 41, 43 and the liquid sample S that make up the sample are in direct contact with each other, the sample can be exchanged as compared to the case where the sample cell is inserted into the measurement light path such as the space in the sample chamber as described above. It takes much time and effort, and it takes time to measure a large number of samples while automatically exchanging samples.
[0009] 特許文献 1 ：特開平 5— 3 1 5324号公報 Patent Document 1: Japanese Patent Laid-Open No. 5-3 1 5324
特許文献 2：特開平 5— 302893号公報  Patent Document 2: JP-A-5-302893
非特許文献 1 ： 「ナノ ドロップ ND- 1000 オーバ一ビュー （NanoDrop ND-1000 0verview)」 、 [onl ine]、 米国ナノ ドロップ■テクノロジ一ズ社 (NanoDrop T echnologies), [平成 1 8年 9月 25日検索]、 インタ一ネットく URL ： http:/ /www. nanodrop. com/nd-1000-overvi ew. html>  Non-Patent Document 1: “NanoDrop ND-1000 Overview”, [online], US Nanodrop Technologies, [September 1996 25] Day search], Internet URL: http: / / www. Nanodrop. Com / nd-1000-overvi ew. Html>
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0010] 本発明は上記課題に鑑みて成されたものであり、 その目的とするところは 、 1〜 2 L程度或いはそれ以下のごく微量の液体試料の透過測定を簡便で 安価な構成且つ手軽な操作で以て行うことができる微量液体試料測定用の分 光光度計を提供することである。  [0010] The present invention has been made in view of the above problems, and the object of the present invention is to provide a simple and inexpensive configuration and easy measurement of transmission of a very small amount of liquid sample of about 1 to 2 L or less. It is to provide a spectrophotometer for measuring a small amount of liquid sample that can be carried out by simple operation.
課題を解決するための手段  Means for solving the problem
[0011] 上記課題を解決するために成された本発明は、 空間内に上下方向に測定光 の通過経路を形成する光学系と、 該光学系による測定光の通過経路中に挿入 され液体試料を保持する試料保持部と、 を具備し、 前記液体試料の透過特性 を測定するための分光光度計において、 前記試料保持部は、  The present invention made to solve the above-described problems includes an optical system that forms a measurement light passage in the vertical direction in a space, and a liquid sample that is inserted into the measurement light passage by the optical system. A spectrophotometer for measuring the transmission characteristics of the liquid sample, wherein the sample holding unit comprises:
a)光を透過可能な材料から成り、 上面及び下面がともに水平である試料台 と、  a) a sample stage made of a material that can transmit light, and whose upper and lower surfaces are both horizontal;
b)光を透過可能な材料から成り、 前記試料台の上面上に滴下された液体試 料の上に該上面と所定距離を以て平行な界面を形成するように前記試料台上 に保持される窓板と、  b) A window made of a material capable of transmitting light and held on the sample stage so as to form an interface parallel to the upper surface with a predetermined distance on the liquid sample dropped on the upper surface of the sample stage. The board,
から成り、 前記試料台の上面に液体試料を滴下した後に、 前記窓板の下面 が前記試料台の上面から所定距離となる位置まで両者を近接させて前記試料 台の上面と前記窓板の下面とに液体試料を接触させた状態でその上方向又は 下方向から測定光を照射して下方向又は上方向に透過した光を測定すること を特徴としている。 And after dropping a liquid sample on the upper surface of the sample table, the lower surface of the window plate is brought close to a position at a predetermined distance from the upper surface of the sample table. In a state in which a liquid sample is in contact with the upper surface of the table and the lower surface of the window plate, the measurement light is irradiated from above or below to measure the light transmitted downward or upward.
[0012] 試料台及び窓板を構成する材料はできるだけ透光性が高いものであること が望ましく、 また特に試料台はその上面に直接液体試料が滴下されることか ら、 この液体試料の液滴の重量を受けても変形しない程度の硬度を有してい る必要がある。 こうしたことから例えば石英ガラスなどを材料として用いる とよい。 具体的には、 試料台としてはガラス製又はプラスチック製の光ファ ィバを適宜の長さに切断して用いることができる。  [0012] It is desirable that the material constituting the sample stage and the window plate be as highly translucent as possible. In particular, since the liquid sample is dropped directly on the upper surface of the sample stage, the liquid sample liquid It must be hard enough not to be deformed by the weight of the drop. For this reason, for example, quartz glass may be used as the material. Specifically, a glass or plastic optical fiber can be cut into an appropriate length and used as a sample stage.
[0013] 本発明に係る分光光度計において試料保持部に液体試料をセッ卜する際に は、 窓板を試料台上方から退避させた状態又は障害にならない程度まで両者 の間隔を離した状態で、 試料台上面にピぺット等で液体試料を微量滴下する 。 滴下された液体試料は液体の表面張力によって試料台上面上で盛り上がつ た液滴状となる。 その後、 窓板をその下面が試料台の上面から所定距離にな るまで降下させると、 窓板の下面に液滴上面が接触し、 窓板下面と試料台上 面との間の空間に液体試料が保持される。 その上面は液体試料と窓板との界 面、 下面は液体試料と試料台との界面となる。 このようにして液体試料を上 下からサンドィツチ状に挟む窓板と試料台とは空間内で測定光の通過経路中 に置かれるため、 測定光は試料を上下方向 （上から下に又はその逆） に通過 し、 上記所定距離が測定の光路長となる。  In the spectrophotometer according to the present invention, when the liquid sample is set in the sample holder, the window plate is retracted from above the sample stage or in a state where the distance between the two is separated to the extent that it does not become an obstacle. Apply a small amount of liquid sample to the top of the sample table with a pipette. The dropped liquid sample is formed into a droplet that rises on the upper surface of the sample table due to the surface tension of the liquid. After that, when the lower surface of the window plate is lowered until the lower surface reaches a predetermined distance from the upper surface of the sample table, the upper surface of the liquid droplet comes into contact with the lower surface of the window plate, and liquid is introduced into the space between the lower surface of the window plate and the upper surface of the sample table. The sample is retained. The upper surface is the interface between the liquid sample and the window plate, and the lower surface is the interface between the liquid sample and the sample stage. In this way, the window plate that sandwiches the liquid sample from above and below and the sample stage are placed in the passage of measurement light in the space, so that the measurement light moves the sample up and down (from top to bottom or vice versa). ) And the above predetermined distance becomes the optical path length of the measurement.
発明の効果  The invention's effect
[0014] 本発明に係る分光光度計によれば、 試料保持部に保持する液体試料は 1〜  [0014] According to the spectrophotometer according to the present invention, the liquid sample held in the sample holder is 1 to
2 U L程度又はそれ以下のごく微量でよいから、 生体試料等の微量液体試料 の分析に好適である。 また、 試料の準備として試料台の上面に液体試料を滴 下すればよいので、 分析に関わる作業が非常に簡単で手間が掛からない。 ま た、 試料台の上面、 窓板の下面等、 液体試料が接触する部位は平面であるた め、 拭き取りや洗浄液による洗浄作業も簡単に行えるし、 乾燥もし易い。  Since a trace amount of about 2 UL or less is sufficient, it is suitable for analyzing a trace amount liquid sample such as a biological sample. In addition, the liquid sample only needs to be dropped on the upper surface of the sample stage as a sample preparation, so the work involved in the analysis is very simple and labor-saving. In addition, the parts that come into contact with the liquid sample, such as the upper surface of the sample stage and the lower surface of the window plate, are flat, so that wiping and cleaning with a cleaning solution can be performed easily and are easy to dry.
[0015] また、 上述したような光ファイバの端面間に液体試料を保持する構成とは 異なり、 測定光学系等、 装置本体には液体試料が接触しないので、 高価な装 置本体に傷を付けたり汚したりしにくく、 保守■点検の負担が増加すること もない。 また、 試料をセットしたり試料を交換したりするために測定光経路 を形成する光学系自体を移動させずに済むので、 測定光学系は固定状態でよ く構造が簡単でコストも安価にできる。 もちろん、 投光側光ファイバと受光 側光ファイバとの光軸合わせも不要であるので、 光軸のずれによる光量の損 失のおそれもない。 さらにまた、 手作業又は自動のいずれにおいても試料交 換が容易であり、 分析のスループッ卜の向上が可能である。 [0015] Also, the configuration for holding the liquid sample between the end faces of the optical fiber as described above. On the other hand, since the liquid sample does not come into contact with the main body of the measurement optical system or the like, it is difficult to damage or contaminate the expensive main body of the apparatus, and the burden of maintenance and inspection does not increase. In addition, it is not necessary to move the optical system that forms the measurement light path in order to set the sample or replace the sample, so the measurement optical system can be fixed and simple in structure and can be inexpensive. . Of course, since there is no need to align the optical axes of the light emitting side optical fiber and the light receiving side optical fiber, there is no risk of loss of light quantity due to the deviation of the optical axis. Furthermore, sample replacement is easy either manually or automatically, and analysis throughput can be improved.
[001 6] 前述のように本発明に係る分光光度計では、 試料台の上面と窓板の下面と の間の距離が測定光路長となるため、 正確な測定を行うにはその距離の設定 精度を高める必要がある。 そこで、 本発明の一態様として、 前記試料台と前 記窓板との間の空間に設置された規制部材に前記試料台及び前記窓板そのも の又はそれらをそれぞれ保持する部材が当接することで、 前記試料台上面と 前記窓板下面との間の距離が所定距離に設定される構成とするとよい。  [001 6] As described above, in the spectrophotometer according to the present invention, the distance between the upper surface of the sample table and the lower surface of the window plate is the measurement optical path length. Need to increase accuracy. Therefore, as one aspect of the present invention, the sample table and the window plate itself or a member that holds them respectively abuts on a regulating member installed in a space between the sample table and the window plate. Thus, the distance between the upper surface of the sample table and the lower surface of the window plate may be set to a predetermined distance.
[001 7] この構成によれば、 試料台の上面に液体試料が滴下された後に窓板と試料 台との距離を徐々に狭めていって規制部材に試料台及び窓板そのもの又はそ れらを保持する部材が当接したときにその距離の狭まりが停止するようにす ることにより、 高い精度で上記距離を設定することができる。 これにより、 測定光路長が高い精度で決まり測定の精度向上を図ることができるとともに 、 構造が簡単であって例えば窓板の移動機構などの停止動作に高い位置精度 を要しないのでコストを抑制するのにも有効である。  [001 7] According to this configuration, after the liquid sample is dropped on the upper surface of the sample table, the distance between the window plate and the sample table is gradually narrowed, and the sample table and the window plate itself or those are used as the regulating member. The distance can be set with high accuracy by stopping the narrowing of the distance when the member holding the contact is made. As a result, the measurement optical path length is determined with high accuracy and the measurement accuracy can be improved, and the cost is reduced because the structure is simple and high positioning accuracy is not required for stopping operation of, for example, the window plate moving mechanism. It is also effective.
[0018] なお、 一般に透過測定では、 例えば試料濃度が高く単位長当たりの吸光度 が大きい場合には測定光路長を短くし、 試料濃度が低く単位長当たりの吸光 度が小さい場合には測定光路長を長く確保することで測定精度を高めること ができる。 そこで、 上記態様の構成において、 前記規制部材は前記所定距離 を変更するためにその高さが変更可能である構成とすれば、 測定光路長を容 易に変更することができる。 こうした変更に伴い測定光学系は全く同一でよ く、 キュべットセルのように光路長の異なる複数の試料セルを用意する必要 もないので、 小さなコス卜の増加で以て測定光路長の変化を実現することが できる。 [0018] In general, in the transmission measurement, for example, when the sample concentration is high and the absorbance per unit length is large, the measurement optical path length is shortened, and when the sample concentration is low and the absorbance per unit length is small, the measurement optical path length is short. Measuring accuracy can be improved by ensuring a long period of time. Therefore, in the configuration of the above aspect, if the height of the regulating member can be changed to change the predetermined distance, the measurement optical path length can be easily changed. With these changes, the measurement optical system may be exactly the same, and it is necessary to prepare multiple sample cells with different optical path lengths, such as cuvette cells. Therefore, the change in the measurement optical path length can be realized with a small increase in cost.
図面の簡単な説明  Brief Description of Drawings
[0019] [図 1]本発明の一実施例である分光光度計に使用される試料保持部の台座部の 上面平面図 （a) 、 及び Α_Α' 矢視線端面図 （b) 。  [0019] FIG. 1 is a top plan view (a) of a pedestal portion of a sample holder used in a spectrophotometer according to an embodiment of the present invention, and (b) an end view taken along line Α_Α ′.
[図 2]図 1に示した試料保持部での液体試料のセッ卜の手順を説明するための 概略側面図。  FIG. 2 is a schematic side view for explaining a procedure for setting a liquid sample in the sample holder shown in FIG.
[図 3]図 1に示した試料保持部で測定光路長を変更する場合の構成を示す概略 側面図。  FIG. 3 is a schematic side view showing the configuration when the measurement optical path length is changed in the sample holder shown in FIG.
[図 4]本実施例の分光光度計の光学系の全体構成図。  FIG. 4 is an overall configuration diagram of the optical system of the spectrophotometer of the present embodiment.
[図 5]測定光路長変更のための回転板を上方から見た平面図。  FIG. 5 is a plan view of the rotating plate for changing the measurement optical path length as viewed from above.
[図 6]測定光路長変更のための別の構成の上面図 （a) 及び正面図 （b) 。  [Fig. 6] Top view (a) and front view (b) of another configuration for changing the measurement optical path length.
[図 7]図 4に示した光学系をベースとした分光光度計の制御系プロック図。  FIG. 7 is a control block diagram of a spectrophotometer based on the optical system shown in FIG.
[図 8]他の実施例の分光光度計における試料保持部の台座部の上面平面図 （ a FIG. 8 is a top plan view of the pedestal of the sample holder in the spectrophotometer of another embodiment (a
) 、 及び Α_Α' 矢視線端面図 （b) 。 ), And Α_Α 'arrow end view (b).
[図 9]従来の微量液体試料の保持方法の説明図。  FIG. 9 is an explanatory diagram of a conventional method for holding a trace liquid sample.
符号の説明  Explanation of symbols
[0020] 1 …光照射部  [0020] 1 ... Light irradiation part
2 …光源  2… Light source
3 …反射鏡  3 ... Reflector
4 …レンズ  4 Lens
5 …試料室  5… Sample chamber
6 …窓板ホルダ  6… Window plate holder
7 …上下駆動機構  7… Vertical drive mechanism
8 …台座ホルダ  8… Pedestal holder
9 …回転板  9… Rotating plate
1 0…軸部  1 0… Shaft
1 1…検出部 1 2■■•レンズ 1 1 ... Detector 1 2 Lens
1 3-- .スリット  1 3-- .Slit
1 4-- •回折格子  1 4--Diffraction grating
1 5-- 出  1 5-- Out
2 0.. •台座部  2 0 .. • Pedestal
2 1■■ •基板  2 1 ■
2 2■■ •導光体  2 2 ■■ Light guide
2 3-- -スぺ一サ  2 3---Spacer
2 4、 24 a〜24 d…補助スぺ  2 4, 24 a to 24 d ... auxiliary spacer
2 5-- •透光性カバー板  2 5-- • Translucent cover plate
2 6--ゼぺット  2 6--Zepette
2 7■■ •裾部  2 7 ■■ Bottom
3 0.. •制御部  3 0 .. • Control part
3 1■■ •測光部  3 1 ■ Metering section
3 2■■ •信号処理部  3 2 ■ Signal processing section
3 3-- •出力部  3 3--Output section
3 4-- •試料保持駆動部  3 4-- • Sample holding drive
3 5-- •拭き取り機構駆動部  3 5-- • Wiping mechanism drive
3 6-- •操作部  3 6-- Operation part
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0021] 本発明に係る分光光度計の一実施例について、 図面を参照して説明する。  An embodiment of a spectrophotometer according to the present invention will be described with reference to the drawings.
まず本実施例の分光光度計に用いられる特徴的な試料保持部の構成について 説明する。 図 1は試料保持部の台座部 20の上面平面図 （a) 、 及び A_A ' 矢視線端面図 （b) である。 図 2はこの試料保持部での液体試料のセット の手順を説明するための概略側面図である。  First, the characteristic configuration of the sample holder used in the spectrophotometer of this embodiment will be described. FIG. 1 is a top plan view (a) of the pedestal 20 of the sample holder and an end view (b) along the line A_A ′. FIG. 2 is a schematic side view for explaining the procedure for setting the liquid sample in the sample holder.
[0022] この試料保持部は大別して、 台座部 20とその上に載せられる透光性カバ —板 （本発明における窓板） 25とから成る。 台座部 20は、 図 1に示すよ うに、 遮光性を有する材料、 例えば金属や樹脂などから成る基板 21に上下 に貫通する円形状の穴が設けられ、 その穴に透光性を有する材料から成る円 柱形状の導光体 （本発明における試料台） 2 2が揷設されてなる。 導光体 2 2の平坦な下面は基板 2 1の下面とほぼ面一にされ、 導光体 2 2の平坦な上 面は基板 2 1の上面よりも高さ d 2だけ上方に突出している。 この例では、 基板 2 1の板厚 d 3は 2 m m、 導光体 2 2の径 d 1は 0 . 8〜 1 . O m mと されている。 この径 d 1は液体試料がその表面で粒状の状態を維持できるよ うに考慮される。 [0022] The sample holder is roughly divided into a pedestal 20 and a translucent cover plate (window plate in the present invention) 25 placed thereon. As shown in FIG. 1, the pedestal 20 is formed on a substrate 21 made of a light-shielding material such as metal or resin. A circular hole penetrating therethrough is provided, and a circular columnar light guide (sample stage in the present invention) 22 made of a material having translucency is provided in the hole. The flat lower surface of the light guide 22 is almost flush with the lower surface of the substrate 21. The flat upper surface of the light guide 22 protrudes above the upper surface of the substrate 21 by a height d2. . In this example, the thickness d 3 of the substrate 21 is 2 mm, and the diameter d 1 of the light guide 22 is 0.8 to 1. O mm. This diameter d 1 is taken into account so that the liquid sample can maintain a granular state on its surface.
[0023] また、 導光体 2 2はその上面に液体試料を直接滴下することから、 この液 滴の重量によって変形することのない或る程度の硬度を有し、 且つ高透光性 であることが望ましく、 例えば石英ガラスなどを利用することができるがプ ラスチックでもよい。 導光体 2 2として、 例えば適宜の長さに切断した光フ アイバ （光ファイバ素線） を利用するができる。 また、 透光性カバ一板 2 5 も同様に石英ガラスやプラスチックなどから成るものとすることができる。 さらにまた、 導光体 2 2の上面 （つまり接液面） 及び下面は光学研磨を施す ことにより、 光の散乱を軽減するとともに接液面での表面張力を高めるよう にすることが望ましい。 また、 導光体 2 2の上面は液体試料が広がらずに粒 状にかたまるように撥水加工処理を施すことが望ましい。  In addition, since the liquid sample directly drops a liquid sample on the upper surface of the light guide 22, the light guide 22 has a certain degree of hardness that is not deformed by the weight of the liquid drop, and is highly translucent. For example, quartz glass can be used, but plastic may be used. As the light guide 22, for example, an optical fiber (optical fiber) cut to an appropriate length can be used. Similarly, the translucent cover plate 25 can also be made of quartz glass, plastic, or the like. Furthermore, it is desirable to optically polish the upper surface (that is, the liquid contact surface) and the lower surface of the light guide 22 so as to reduce light scattering and increase the surface tension on the liquid contact surface. In addition, it is desirable that the upper surface of the light guide 22 is subjected to a water repellent treatment so that the liquid sample does not spread and is gathered into a granular shape.
[0024] 上記構成の試料保持部に液体試料をセットする際には、 図 2 ( a ) に示す ように、 基板 2 1の上面には上記高さ d 2よりも大きな適宜の高さ d 4のス ぺ_サ (本発明における規制部材） 2 3が配置される。 そして、 透光性カバ 一板 2 5を邪魔にならない位置まで上昇させた或いは台座部 2 0の上方から 取り除いた状態で、 ピぺット 2 6などを用いて微量の液体試料 Sを導光体 2 2の上面に滴下する。 滴下された液体試料 Sは、 表面張力によって導光体 2 2の上面で粒状となる。  When a liquid sample is set in the sample holder having the above-described configuration, an appropriate height d 4 larger than the height d 2 is provided on the upper surface of the substrate 21, as shown in FIG. 2 (a). Spacers (regulating members in the present invention) 23 are arranged. Then, with the translucent cover plate 25 raised to an unobstructed position or removed from above the pedestal 20, a small amount of liquid sample S is guided using a pipette 26. Drop on top of body 2 2. The dropped liquid sample S becomes granular on the upper surface of the light guide 22 due to surface tension.
[0025] その上から図 2 ( b ) に示すように透光性カバ一板 2 5を被せ、 透光性力 バー板 2 5の下面がスぺ一サ 2 3の上面に当接するまで降下させる。 前述の ように、 スぺ一サ 2 3の高さ d 4は導光体 2 2の突出高さ d 2よりも大きい ため、 透光性カバ一板 2 5の下面と導光体 2 2の上面との間には d 4 - d 2 の距離の間隙が形成され、 その間隙に液体試料 Sが満たされるように保持さ れる （図 2 ( c ) 参照） 。 即ち、 液体試料 Sは透光性カバー板 2 5と導光体 2 2とでサンドィツチ状に挟まれ、 透光性カバ一板 2 5の下面が液体試料 S の上の界面、 導光体 2 2の上面が液体試料 Sの下の界面となる。 以上がこの 試料保持部における液体試料のセット方法である。 [0025] As shown in Fig. 2 (b), cover the translucent cover plate 25 and lower it until the lower surface of the translucent force bar plate 25 contacts the upper surface of the spacer 23. Let As described above, since the height d 4 of the spacer 23 is larger than the protruding height d 2 of the light guide 22, the lower surface of the translucent cover plate 25 and the light guide 22 D 4-d 2 between top surface A gap is formed at a distance of (3) and is held so that the liquid sample S is filled in the gap (see FIG. 2 (c)). That is, the liquid sample S is sandwiched between the translucent cover plate 25 and the light guide 22, and the lower surface of the translucent cover plate 25 is the interface above the liquid sample S, the light guide 2 The upper surface of 2 becomes the lower interface of the liquid sample S. The above is the method for setting the liquid sample in the sample holder.
[0026] 上記のように準備された液体試料 Sの吸光度や透過率などの透過特性を測 定する際には、 液体試料 Sに上方から垂直下方に向けて測定光を照射する。 この測定光の光軸は円柱形状の導光体 2 2のほぼ中心軸に沿つて進むように 設定されており、 透光性カバー板 2 5と導光体 2 2の間に満ちた液体試料 S 中を通過した透過光が真下に抜ける。 したがって、 d 4 _ d 2の距離が液体 試料 Sの測定の光路長 L 1 となり （図 3 ( a ) 参照） 、 最初に滴下された液 体試料の量に依存せずに光路長は一義的に且つ精度良く定まる。  [0026] When measuring the transmission characteristics such as absorbance and transmittance of the liquid sample S prepared as described above, the liquid sample S is irradiated with measurement light from above to vertically downward. The optical axis of this measurement light is set so as to travel along the substantially central axis of the cylindrical light guide 22, and the liquid sample filled between the translucent cover plate 25 and the light guide 22. S The transmitted light that has passed through it goes straight down. Therefore, the distance of d 4 _ d 2 becomes the optical path length L 1 for the measurement of the liquid sample S (see Fig. 3 (a)), and the optical path length is unambiguous regardless of the amount of the liquid sample dropped first. And accurately determined.
[0027] このように測定光路長はスぺ一サ 2 3の高さ d 4に依存するから、 例えば 図 3 ( c ) に示すようにスぺ一サ 2 3 ' を高さの相違するものに変更するこ とにより、 測定光路長を容易に変更することができる。 図 3 ( c ) の例では 、 光路長は L 2に拡大されている。 また、 スぺ一サ 2 3を交換する代わりに 、 図 3 ( b ) に示す如くスぺ一サ 2 3の上に別の補助スぺ一サ 2 4を揷入す ることで全体の高さを変更するようにしてもよい。 一般に、 測定光路長を変 更したいのは試料濃度が異なる場合であるが、 無段階に光路長を変更可能と しておく必要はなく、 たかだか数段階程度に変更可能であれば十分である。 したがって、 高さの相違するスぺ一ザに交換する方法でも、 それほど多数の スぺ—サを用意してお <必要はない。 なお、 液体試料の液量が 1〜2 Lで ある場合には、 光路長は 0 . 2〜0 . 7 m m程度の範囲が適切である。  [0027] Since the measurement optical path length depends on the height d 4 of the spacer 23, as described above, for example, as shown in Fig. 3 (c), the spacer 2 3 'has a different height. By changing to, the measurement optical path length can be easily changed. In the example of Fig. 3 (c), the optical path length is extended to L2. Also, instead of replacing the spacer 23, the entire height can be increased by inserting another auxiliary spacer 24 on the spacer 23 as shown in Fig. 3 (b). You may make it change the length. In general, it is desirable to change the measurement optical path length when the sample concentration is different, but it is not necessary to change the optical path length steplessly, and it is sufficient if it can be changed to a few steps at most. Therefore, it is not necessary to prepare a large number of spacers even when replacing with spacers of different heights. When the amount of the liquid sample is 1 to 2 L, the optical path length is suitably in the range of about 0.2 to 0.7 mm.
[0028] 次に、 上記試料保持部を使用して液体試料の透過特性を測定する分光光度 計の一実施例について、 図 4、 図 5を参照して説明する。 図 4は本実施例の 分光光度計の光学系の全体構成図である。 Next, an embodiment of a spectrophotometer that measures the transmission characteristics of a liquid sample using the sample holder will be described with reference to FIG. 4 and FIG. FIG. 4 is an overall configuration diagram of the optical system of the spectrophotometer of this embodiment.
[0029] この分光光度計では、 光照射部 1から鉛直下向きに測定光が出射され、 試 料を通過した透過光を分光検出する検出部 1 1は試料室 5を挟んで光照射部 1の下方に配置されている。 即ち、 試料室 5が設置される空間内を上から下 向きに測定光が進行する光学系となっている。 具体的には、 光照射部 1にお いて光源 2から出射された光は反射鏡 3で反射されて下向きに方向を変えレ ンズ 4により集光されて測定光として試料保持部に保持される液体試料 Sに ほぼ真上から照射される。 液体試料 Sは上述したように透光性カバー板 2 5 と導光体 2 2との間に保持されている。 台座部 2 0は台座ホルダ 8により軸 部 1 0に対しその位置が固定されており、 一方、 透光性カバ一板 2 5はカバ 一板ホルダ 6に保持され、 上下駆動機構 7により軸部 1 0に沿って上下動可 能となっている。 In this spectrophotometer, the measurement light is emitted vertically downward from the light irradiating unit 1, and the detecting unit 11 that spectrally detects the transmitted light that has passed through the sample is located between the sample chamber 5 and the light irradiating unit 1 is arranged below. That is, an optical system in which measurement light travels from the top to the bottom in the space in which the sample chamber 5 is installed. Specifically, the light emitted from the light source 2 in the light irradiating unit 1 is reflected by the reflecting mirror 3, changes its direction downward, and is collected by the lens 4 and is held in the sample holding unit as measurement light. The liquid sample S is irradiated almost from above. The liquid sample S is held between the translucent cover plate 25 and the light guide 22 as described above. The position of the pedestal portion 20 is fixed to the shaft portion 10 by the pedestal holder 8. On the other hand, the translucent cover plate 25 is held by the cover plate holder 6, and the shaft portion is supported by the vertical drive mechanism 7. It can move up and down along 10.
[0030] さらに、 軸部 1 0を中心に回動自在である円板状の回転板 9には、 周方向 に互いに離して高さの相違する複数の補助スぺ一サ 2 4が装着されている。 図 5はこの回転板 9を上方から見た平面図である。 軸部 1 0の周りに回転板 9を回動させて所望の高さの補助スぺ一サ 2 4 a〜2 4 d (但し、 補助スぺ ーサ 2 4 aは回転板 9自体の厚さのみが補助スぺーザとして機能する） を基 板 2 1の上に挿入する。 この例では台座部 2 0ではなく窓板ホルダ 6の下面 にスぺ一サ 2 3が取り付けられ、 窓板ホルダ 6が降下したときにスぺ一サ 2 3の下面が基板 2 1上面又はその間隙に挿入される補助スぺ一サ 2 4に当接 するように構成されている。  [0030] Furthermore, a plurality of auxiliary spacers 24 having different heights apart from each other in the circumferential direction are mounted on a disc-shaped rotating plate 9 that is rotatable about the shaft portion 10. ing. FIG. 5 is a plan view of the rotating plate 9 as viewed from above. Auxiliary spacers 2 4 a to 2 4 d of desired height by rotating the rotating plate 9 around the shaft portion 10 (however, the auxiliary spacer 2 4 a is the thickness of the rotating plate 9 itself) Insert only the top of the board 21. In this example, the spacer 23 is attached to the lower surface of the window plate holder 6 instead of the pedestal 20, and when the window plate holder 6 is lowered, the lower surface of the spacer 23 is the upper surface of the substrate 21 or its It is configured to abut against the auxiliary spacer 24 inserted into the gap.
[0031 ] 透光性カバー板 2 5を上げた状態で試料保持部の導光体 2 2の上面に前述 したように分析対象である液体試料を滴下し、 その後に上下駆動機構 7によ りカバ一板ホルダ 6を下降させる。 すると、 スぺ一サ 2 3の下面が基板 2 1 上に位置している補助スぺ一サ 2 4 a〜2 4 dのいずれかに当接し、 その位 置でカバー板ホルダ 6つまりは透光性カバー板 2 5の降下が停止する。 これ により、 透光性カバー板 2 5と導光体 2 2との間に液体試料 Sが保持され、 その測定光路長も補助スぺ一サ 2 4 a〜2 4 dに応じて定まる。  [0031] With the translucent cover plate 25 raised, the liquid sample to be analyzed is dropped onto the upper surface of the light guide 22 of the sample holder as described above, and then the vertical drive mechanism 7 Lower the cover plate holder 6. Then, the lower surface of the spacer 23 is brought into contact with one of the auxiliary spacers 2 4 a to 2 4 d located on the substrate 21, and the cover plate holder 6, that is, the transparent The descent of the light cover plate 2 5 stops. Thereby, the liquid sample S is held between the translucent cover plate 25 and the light guide 22, and the measurement optical path length is also determined according to the auxiliary spacers 24 a to 24 d.
[0032] こうして用意された液体試料 Sに対し、 図 4に示したように、 測定光は真 上から透光性カバー板 2 5を通して照射される。 液体試料 Sを通過する過程 で該試料 S中の試料成分に応じた波長成分が吸収を受け、 透過光が導光体 2 2を経て下方に出射する。 また、 散乱光などの不要な光の多くは遮光性を有 する基板 2 1で遮られるため、 下方に出射しない。 透過光は検出部 1 1にお いてレンズ 1 2で集光され、 スリット 1 3で光域が制限された後に回折格子As shown in FIG. 4, the liquid sample S thus prepared is irradiated with measurement light from directly above through the translucent cover plate 25. In the process of passing through the liquid sample S, the wavelength component corresponding to the sample component in the sample S is absorbed, and the transmitted light is guided to the light guide 2 It goes out downward through 2. In addition, most of the unnecessary light such as scattered light is blocked by the light-blocking substrate 21 and therefore does not exit downward. The transmitted light is collected by the lens 1 2 at the detector 1 1, and after the light region is limited by the slit 1 3, the diffraction grating
1 4に導入される。 この回折格子 1 4で透過光は波長分散され、 その波長分 散光は例えば C C Dリニアセンサ等であるマルチチャンネル型の検出器 1 5 によりほぼ同時に検出される。 もちろん、 回折格子 1 4を回動させることで 検出器 1 5に入射する光の波長が走査される光学系とする等、 光学系の構成 は適宜に変更することができる。 また、 ダブルビームの構成とすることもで さる。 Introduced in 1-4. The transmitted light is wavelength-dispersed by the diffraction grating 14, and the wavelength-dispersed light is detected almost simultaneously by a multi-channel detector 15 such as a C CD linear sensor. Of course, the configuration of the optical system can be changed as appropriate, such as turning the diffraction grating 14 to an optical system that scans the wavelength of light incident on the detector 15. A double beam configuration is also possible.
[0033] 以上のようにして、 検出器 1 5では液体試料 Sの透過特性を反映した検出 信号を得ることができるから、 後述する信号処理部において例えば所定の波 長範囲の吸光スぺク トルを作成することができる。  [0033] Since the detector 15 can obtain a detection signal reflecting the transmission characteristics of the liquid sample S as described above, an absorption spectrum having a predetermined wavelength range, for example, can be obtained in a signal processing unit described later. Can be created.
[0034] 図 4で明らかなように、 透光性カバ一板 2 5と台座部 2 0とで構成される 試料保持部は測定光が通過する空間内 （図 4では試料室 5内） に配設されて いるため、 光照射部 1や検出部 1 1などの測定光学系に影響を与えることな く容易に入れ替えることができ、 それによつて測定対象の試料を次々に交換 することができる。 この入れ替えは台座部 2 0のみを入れ替えることもでき るし、 台座部 2 0と透光性カバ一板 2 5とを組として入れ替えることもでき る。 但し、 コンタミネ一シヨンを回避するために、 台座部 2 0のみを入れ替 え、 透光性カバー板 2 5は共通のものとする場合に、 液体試料が接触する透 光性カバー板 2 5の下面は測定の度に洗浄 （又は拭き取り） を行う必要があ るが、 いずれにしても簡単な機構を付加することにより試料の自動交換を実 現することができる。  [0034] As is apparent from FIG. 4, the sample holder composed of the translucent cover plate 25 and the pedestal 20 is located in the space through which the measurement light passes (in the sample chamber 5 in FIG. 4). Because it is arranged, it can be easily replaced without affecting the measurement optical system such as the light irradiating unit 1 and the detecting unit 11, thereby allowing the samples to be measured to be replaced one after another. . In this replacement, only the pedestal portion 20 can be replaced, or the pedestal portion 20 and the translucent cover plate 25 can be replaced as a pair. However, in order to avoid contamination, only the pedestal 20 is replaced, and the translucent cover plate 25 is used in common. In this case, cleaning (or wiping) is required for each measurement. In any case, automatic replacement of the sample can be realized by adding a simple mechanism.
[0035] なお、 試料濃度に応じて補助スぺーサ 2 4 a〜2 4 dは適宜に選択すれば よいが、 上述のような回動式の切替機構ではなく、 図 6に示すように厚さの 相違する補助スぺ一サ 2 4 a〜2 4 dを一直線上に配列してその配列方向に 沿って往復動可能な機構を用いても、 同様に簡単に測定光路長を変更するこ とができる。 [0036] 図 7は図 4に示した光学系をベースとする分光光度計の一実施例による制 御系ブロック図である。 この分光光度計では、 試料の測定を効率良く行うた めに試料の滴下以外の各種作業が自動的に行われるように構成されている。 マイクロコンピュータ等を含む制御部 3 0は、 導光性カバー板 2 2を上下動 させる上下動駆動機構 7に含まれるモータなどを駆動する試料保持駆動部 3[0035] Note that the auxiliary spacers 24a to 24d may be appropriately selected according to the sample concentration. However, the auxiliary spacers 24a to 24d may be appropriately selected. Even if the auxiliary spacers 2 4 a to 24 d with different heights are arranged in a straight line and a mechanism capable of reciprocating along the arrangement direction is used, the measurement optical path length can be easily changed in the same manner. You can. FIG. 7 is a control system block diagram of an embodiment of a spectrophotometer based on the optical system shown in FIG. This spectrophotometer is configured so that various operations other than the dropping of the sample are automatically performed in order to efficiently measure the sample. The control unit 30 including a microcomputer or the like includes a sample holding drive unit 3 that drives a motor and the like included in a vertical movement drive mechanism 7 that moves the light guide cover plate 22 up and down.
4、 導光性カバ一板 2 5の下面及び導光体 2 2の上面に付着している測定済 みの液体試料を拭き取るための機構を駆動するための拭き取り機構駆動部 34. Wiping mechanism drive unit 3 for driving the mechanism for wiping the measured liquid sample adhering to the lower surface of the light guide cover plate 25 and the upper surface of the light guide 22
5、 上記光照射部 1や検出部 1 1などを含む測光部 3 1、 を予め設定された シーケンスに従って制御する。 また制御部 3 0に接続された操作部 3 6は分 析開始や一時中止等の指示を与えるものである。 測光部 3 1で得られた検出 信号は信号処理部 3 2で処理されて吸光スぺク トルなどが作成され、 その結 果が出力部 3 3より出力される。 5. Control the photometry unit 31 including the light irradiation unit 1 and the detection unit 11 according to a preset sequence. An operation unit 36 connected to the control unit 30 gives an instruction to start or temporarily stop the analysis. The detection signal obtained by the photometry unit 31 is processed by the signal processing unit 32 to create an absorption spectrum, and the result is output from the output unit 33.
[0037] 本装置は、 測定待ち （スタンドバイ） 状態では、 透光性カバー板 2 5が上 昇した状態にある。 この状態で分析担当者はマイクロピぺットにより微量の 液体試料を導光体 2 2の上面に滴下し、 操作部 3 6より測定開始を指示する 。 すると、 この指示を受けた制御部 3 0は、 試料保持駆動部 3 4により透光 性カバ一板 2 5を所定高さまで降下させる、 これにより、 上述したように導 光体 2 2と透光性カバー板 2 5との間に液体試料が保持される。 次に、 制御 部 3 0は測光部 3 1に指示を与え、 液体試料に測定光を照射し、 その透過光 の強度を測定する。 この測定時の波長範囲や波長ステップなどは予め設定し た測定条件に則って決められる。 そして測定が終了すると、 試料保持駆動部 3 4により透光性カバー板 2 5が所定高さまで上昇される。 その後、 拭き取 り機構駆動部 3 5によりウェスが装着された拭き取り用へッドが移動され、 導光体 2 2の上面及び透光性カバー板 2 5の下面に付着している液体試料が 除去される。 その後、 拭き取り用へッドは導光体 2 2と透光性カバー板 2 5 との間から退避され、 さらに試料保持駆動部 3 4により透光性カバー板 2 5 が最大高さまで上昇された状態でスタンドバイ状態に移行し、 次の測定の指 示を待つ。 なお、 拭き取り機構については、 本出願人が特願 2 0 0 7— 2 0 1 8 7 6号などで提案している機構を用いることができる。 [0037] This apparatus is in a state in which the translucent cover plate 25 is raised in the measurement standby (standby) state. In this state, the person in charge of analysis drops a small amount of liquid sample onto the upper surface of the light guide 22 with a micropipette, and instructs the start of measurement from the operation unit 36. Then, the control unit 30 that has received this instruction lowers the translucent cover plate 25 to a predetermined height by the sample holding drive unit 34, whereby the light guide 22 and the translucent plate are transmitted as described above. A liquid sample is held between the protective cover plates 25 and 5. Next, the control unit 30 gives an instruction to the photometry unit 31, irradiates the liquid sample with measurement light, and measures the intensity of the transmitted light. The wavelength range and wavelength step during this measurement are determined according to preset measurement conditions. When the measurement is completed, the translucent cover plate 25 is raised to a predetermined height by the sample holding drive unit 34. After that, the wiping head with the waste attached is moved by the wiping mechanism driving unit 35, and the liquid sample attached to the upper surface of the light guide 22 and the lower surface of the translucent cover plate 25 is removed. Removed. Thereafter, the wiping head was retracted from between the light guide 22 and the translucent cover plate 2 5, and the translucent cover plate 2 5 was raised to the maximum height by the sample holding drive unit 3 4. Enter standby mode and wait for the next measurement instruction. Regarding the wiping mechanism, the applicant has applied for a patent application 2 0 0 7− 2 0 The mechanism proposed in 1 8 7 6 etc. can be used.
[0038] 上述したように導光体 2 2の上面に残った液体試料を拭き取るために、 紙 タオルなどから成るウェスをほぼ水平に移動させながら導光体 2 2の上面に 接触させる場合、 試料保持部が図 1に示した構成であると、 導光体 2 2の上 面の略 9 0 ° のコーナ一にウェスが引掛かり易く、 ウェスのスムーズな移動 に支障をきたしたり、 ウェスの繊維が残ったりすることがあり得る。 そこで 、 特に、 液体試料の拭き取りの容易性を考慮した場合に、 試料保持部の構造 を図 8に示すように変形するとよい。 図 8において図 1に記載の構成要素と 同一のものには同一の符号を付している。 この変形例の構成では、 基板 2 1 から上方に突出した円柱状の導光体 2 2の周囲に周面が円錐状の裾部 2 7を 設けている。 導光体 2 2と裾部 2 7とは一体でも別体でもよい。 この構成に より、 導光体 2 2の上面のコーナ一にウェスが引掛かりにくくなるので、 拭 き取りへッドのスムーズな移動が確保され、 ウェスの繊維が導光体 2 2に付 着することも防止できる。 [0038] As described above, in order to wipe off the liquid sample remaining on the upper surface of the light guide 22, when the waste made of paper towel or the like is moved substantially horizontally and brought into contact with the upper surface of the light guide 22, the sample If the holding portion has the configuration shown in FIG. 1, the waste is likely to be caught on the approximately 90 ° corner of the upper surface of the light guide 22 and hinders the smooth movement of the waste. May remain. Therefore, in particular, when considering the ease of wiping off the liquid sample, the structure of the sample holder may be modified as shown in FIG. In FIG. 8, the same components as those shown in FIG. 1 are denoted by the same reference numerals. In the configuration of this modified example, a skirt portion 27 having a conical peripheral surface is provided around a cylindrical light guide 22 protruding upward from the substrate 21. The light guide 2 2 and the skirt 2 7 may be integrated or separated. This configuration makes it difficult for the waste to get caught in the corner on the upper surface of the light guide 22, ensuring smooth movement of the wiping head and attaching the waste fibers to the light guide 22. Can also be prevented.
[0039] また、 上記説明では液体試料の滴下は作業者が行うようにしており、 自動 化されていない。 これは、 一般にマイクロピぺットを用いた 1 L程度以下 のごく微量の液体試料の採取及び滴下は安価な装置では難しいためであるが 、 もちろん、 これも自動化しても構わない。 [0039] In the above description, the dropping of the liquid sample is performed by the operator, and is not automated. This is because collecting and dropping a very small amount of a liquid sample of about 1 L or less using a micropipette is generally difficult with an inexpensive apparatus, but of course, this may be automated.
[0040] なお、 上記実施例は本発明の一例にすぎず、 本発明の趣旨の範囲で適宜変 形、 修正、 追加等を行っても本願請求の範囲に包含されることは当然である [0040] It should be noted that the above-described embodiment is merely an example of the present invention, and it is a matter of course that modifications, corrections, additions, and the like are appropriately included in the scope of the present application within the scope of the present invention.

Claims

請求の範囲 The scope of the claims
[1 ] 空間内に上下方向に測定光の通過経路を形成する光学系と、 該光学系によ る測定光の通過経路中に挿入され液体試料を保持する試料保持部と、 を具備 し、 前記液体試料の透過特性を測定するための分光光度計において、 前記試 料保持部は、  [1] An optical system that forms a measurement light passage in the vertical direction in the space, and a sample holder that is inserted into the measurement light passage by the optical system and holds a liquid sample. In the spectrophotometer for measuring the transmission characteristics of the liquid sample, the sample holding unit includes:
a)光を透過可能な材料から成り、 上面及び下面がともに水平である試料台 と、  a) a sample stage made of a material that can transmit light, and whose upper and lower surfaces are both horizontal;
b)光を透過可能な材料から成り、 前記試料台の上面上に滴下された液体試 料の上に該上面と所定距離を以て平行な界面を形成するように前記試料台上 に保持される窓板と、  b) A window made of a material capable of transmitting light and held on the sample stage so as to form an interface parallel to the upper surface with a predetermined distance on the liquid sample dropped on the upper surface of the sample stage. The board,
から成り、 前記試料台の上面に液体試料を滴下した後に、 前記窓板の下面 が前記試料台の上面から所定距離となる位置まで両者を近接させて前記試料 台の上面と前記窓板の下面とに液体試料を接触させた状態でその上方向又は 下方向から測定光を照射して下方向又は上方向に透過した光を測定すること を特徴とする分光光度計。  After dropping a liquid sample on the upper surface of the sample table, the lower surface of the window plate is brought close to the position where the lower surface of the window plate is a predetermined distance from the upper surface of the sample table, and the upper surface of the sample table and the lower surface of the window plate A spectrophotometer characterized by measuring the light transmitted downward or upward by irradiating measurement light from above or below in a state in which a liquid sample is in contact with the liquid sample.
[2] 請求項 1に記載の分光光度計において、 前記試料台と前記窓板との間の空 間に設置された規制部材に前記試料台及び前記窓板そのもの、 又はそれらを それぞれ保持する部材が当接することで、 前記試料台上面と前記窓板下面と の間の距離が所定距離に設定されることを特徴とする分光光度計。  [2] The spectrophotometer according to claim 1, wherein the sample table and the window plate themselves are held by a regulating member installed in the space between the sample table and the window plate, or members that respectively hold them. , The distance between the upper surface of the sample table and the lower surface of the window plate is set to a predetermined distance.
[3] 請求項 2に記載の分光光度計において、 前記規制部材は前記所定距離を変 更するためにその高さが変更可能であることを特徴とする分光光度計。  [3] The spectrophotometer according to claim 2, wherein the height of the restricting member is changeable in order to change the predetermined distance.
[4] 請求項 1又は 2に記載の分光光度計において、 前記窓板の下面と前記試料 台の上面との間の距離が変化するように少なくともいずれか一方を上下方向 に移動させる移動手段と、 前記試料台の上面と前記窓板の下面とに液体試料 を接触させた状態でその上方向又は下方向から測定光を照射して下方向又は 上方向に透過した光を測定する測光手段と、 をさらに備えることを特徴とす る分光光度計。  [4] The spectrophotometer according to claim 1 or 2, wherein at least one of the spectrophotometers moves in a vertical direction so that a distance between a lower surface of the window plate and an upper surface of the sample stage changes. A photometric means for measuring the light transmitted downward or upward by irradiating the measurement light from the upper or lower direction with the liquid sample in contact with the upper surface of the sample stage and the lower surface of the window plate; A spectrophotometer, further comprising:
[5] 請求項 4に記載の分光光度計において、 前記移動手段により前記窓板の下 面と前記試料台の上面との距離が所定距離になるように少なくとも一方を移 動させ、 前記試料台の上面と前記窓板の下面とに液体試料が接触した状態で 、 前記測光手段により、 その上方向又は下方向から測定光を照射して下方向 又は上方向に透過した光を測定するように、 それら各手段の動作を制御する 制御手段をさらに備えることを特徴とする分光光度計。 [5] The spectrophotometer according to claim 4, wherein the moving means is provided below the window plate. At least one is moved so that the distance between the surface and the upper surface of the sample table is a predetermined distance, and the liquid sample is in contact with the upper surface of the sample table and the lower surface of the window plate, A spectrophotometer further comprising control means for controlling the operation of each means so as to measure the light transmitted downward or upward by irradiating the measurement light from the upward or downward direction.
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